Gasoline additive mixture



United States Patel O GASOLINE ADDITIVE MIXTURE Kenneth A. Smith, Homewood, Ill., assignor to Sinclair Refining Company, New York, N.Y., a corporation of ame No Drawing. Application March 7, 1957 Serial No. 644,470

9 Claims. (Cl. 44-53) My invention relates to a new composition of matter which is suitable for use as an additive to gasoline.

It is conventional to add methanol to gasoline in small amount for the purpose of preventing the freezing of water which may be present in the gasoline. Generally,

where methanol is used for this purpose, it is employed in the amount of from about 0.05 to 1% by volume, based upon the volume of the gasoline. It has also been proposed to incorporate small amounts of various trialkyl phosphines into gasoline which contains tetraethyl lead as 1 cals containing from 1 to 3 carbon atoms, primary or secondary butyl radicals or a primary amyl radical. The amount of phosphine added to the leaded gasoline generally amounts to from 0.005 to 0.025% by volume, based upon the volume of the gasoline. This range is approximately 0.2 to 1.0 cc. of the phosphine per gallon of gasoline.

In order to prevent loss, the methyl alcohol and the phosphine are conveniently added to the gasoline near the points from which the gasoline is distributed, and this is most conveniently done by adding a mixture or concentrate containing the methyl alcohol and the phosphine. The methyl alcohol-phosphine mixture is most conveniently stored in iron or steel tanks which are open to the air. When this is done, however, it is found that oxidation of the phosphine to form acidic materials and consequent rusting of the tank take place. This is definitely undesirable, inasmuch as gasoline conventionally contains a metal deactivator, such as N,N'-disalicylidene-1,2-propane-diamine, which serves the function of reacting with any copper present in the gasoline as a contaminant. Copper is deleterious in gasoline in that it reduces the oxygen b omb stability. The efiect of iron as a contaminant in gasoline due to rusting is that the iron as well as copper reacts with the metal deactivator, thereby reducing the amount of deactivator present which can serve the function of reacting with copper.

In accordance with my invention, I have discovered a way in which the oxidation of methanol-phosphine mixtures due to air and the consequent rusting of iron and steelstorage vessels containing them can be substantially retarded. At the same time, it is found that the methanolphosphine mixtures treated in accordance with my inven- I tion are consderably less corrosive to copper, brass and ganate or manganous nitrate, but in their place I can use any of a wide variety of other compounds, such as anhydrous manganous acetate, manganese dichloride tetrahydrate, manganous oxalate dihydrate or trihydrate, manganous orthophosphate trihydrate, manganous sulfate monohydrate, dihydrate or trihydrate, and the like. Hence, my invention involves compositions which consist essentially of from to 98% by volume of methanol and from 20 to 2% by volume of a phosphine of the formula RRR"P wherein R, R and R" are alkyl radicals containing from 1 to 3 carbon atoms, primary and secondary butyl radicals or primary amyl radicals. R, R and R" can be the same or different, and mixtures of the phosphines can also be-used. Among these phosphines which can suitably be utilized are tri-n-butyl phosphine and triethyl phosphine. In addition to the methyl alcohol and phosphine, my composition also contains from about 2.5 to 100 mg. per liter of the manganese compound or salt, and preferably from 15 to 50 mg. per liter. In use, my composition is simply blended into leaded gasoline in amount such that the phosphine added to the gasoline is from about 0.2 to 1.0 cc. per gallon.

In preparing my composition, the manganese compound or salt can first be dissolved in the methanol and the methanol then mixed with the phosphine or mixture of phosphines. Also, if desired, the manganese compound or salt can be dissolved in the methanol and the solution then mixed with the phosphine or mixture of phosphines and a further quantity of methanol. Other methods of preparing my composition will suggest themselves to those skilled in the art.

The following examples illustrate various embodiments which fall within the scope of my invention, and further illustrate the practice thereof.

EXAMPLE I A series of corrosion tests under oxidizing conditions were made by bubbling air through a concentrate composed of by volume of methanol and 5% by volume of tri-n-butyl phosphine in the presence of one or more metals. Corrosition rates were determined by analyzing the concentrates or by measuring the weight loss of the metals. Further information concerning the test conditions and information concerning the test results are set forth in Table I.

In runs 10 through 14, nickel, chromium, manganese and molybdenum (metals which might be present as impurities in steel) were added in trace amounts to portions of the concentrate in the form of powdered nickel, potassium dichromate, potassium permanganate and ammonium molybdate. In43 hours, 4 of the 5 samples subjected to test, including the base concentrate with no additives, had picked up large amounts of iron, exceeding 200 p.p.m., from small ingot iron discs that were present. The concentrate containing potassium permanganate, however, showed no iron pick-up in 43 hours and the test was continued to 162 hours at which time it still showed essentially no iron corrosion. Additional tests with potassium permanganate in various concentrations (runs 18, 20 and 21) also showed no iron corrosion. During one test (run 18) a copper strip was added to the concentrate for the final 42 hours of the test to determine whether potassium permanganate might also eliminate copper corrosion. Copper pick-up of approximately 300 p.p.m. occurred during this time. As N,N-disalicylidene-1,2-propane-diamine (MDA) is at times blended into methanol-phosphine concentrates before they are added to gasoline, a test (run 23) was made with both potassium permanganate and the metal deactivator present. The results of this test showed that potassium permanganate is just as effective in eliminating iron pick-up in this combination.

Other oxidation tests were made in the presence of the ingot iron discs and they showed that an oxidized concentrate already containing large amounts of iron continued to pick-up iron at a steady rate (run 19), and

tive as potassium permanganate in reducing copper and iron corrosion.

EXAMPLE II The various tests performed in accordance with this g zi s g ggg i i jg 5 example were run on a 95% by volume methanol-5% was also mad g glen-051011 by volume tri-n-butyl phosphine mixture by oxidation in th absenceeofnir 5 e z OX1 with air in the manner described in Example I. To study n ir'on dis th on 5 f t 6 the effect of manganous acetate tetrahydrate concentra- Ih 51/ h zg 9 concen 10 tion, a series of oxidation tests were made with concenq i g 2 .2 g g e trations of the manganous acetate tetrahydrate ranging g lg t 2 2 p from 2 /2 to 100 mg. per liter of concentrate. These 5 t a 2 S .3"? p i Iron tests are reported in Table II, as runs 53 through 58. i f 2 1 3 on a es m e iifi The amounts of tri-n-butyl phosphine oxidation and iron t co 0 t a 2 3 g was 2: W1 pick-up in 66 hours were negligible at all concentrations. gg t g i g fi 3 6 a O gg e p Thus, a concentration as low as 15 mg. of manganous test'sh w d e s a g su f f Co g i acetate tetrahydrate per liter of concentrate gives ade- I 2 S e i g t g p ai i g? quate protection against iron pick-up with a large safety I; 29 3 qua 1 g i factor. The data also show that copper attack can also i on aelon o i P 05p me In be substantially reduced by employing a manganous aceours W1 ou po.as.smm p rmangana tate tetrahydrate concentration of at least 15 mg. per liter Concentrates containing only MDA (runs 31 and 32) of concentrate Showed heavy towards copper whlte As a specific illustration of the use of a composition metal, and essentially no corrosion of aluminum and falling within the scope of my invention, a concentrate Monel. Samples of concentrates containing potassium fi t d d f 957 b V lum f meflb permanganate and MDA (runs 35 and 36) showed lower 1S rs g b comlpose T corrosion of white metal, greatly reduced steel corrosion, and and 5 o mm 0 my P 08p 0 and also a substantial reduction in copper corrosion. the Con ntrate 1s added 100 mg. of manganous acetate Other compounds containing manganese were also found tetrahyflrate P htel' of coffcefltrate- The concclltrate to be effective. Manganous acetate (chemically pure wntammg the tetrahydrate 1S Incorporated 1M0 leaded manganous acetate tetrahydrate) and maganous nitrate gasollne 1n the amount of 0.26% by volume, based upon used in runs 44 and 45., respectively, were just as efiecthe volume of the gasoline.

Table l Solution: Oonc.

Methanol 95% 957 95 /1 95) 95 95% from 95%"-.. 95%... 95%. TBP 5% 5 5 5 5 5 5% 5%.

Additives None. Powdered K2CI207 KMnO4 (NH4)2M0O4 KMnO4 None. KMnO4 KMI1O4 DBPC Nickel (Trace). (Trace). (Trace). (Trace). 100 (500 2. 9 (Trace). g-/ -l 1.). 1.). 1.). Test Results: Weight Loss of Metal Specimens- Test Hours 43. 43 43 162 43 114 42 42 42 48. Ingot Fe Disc (Gms. Lost) 2278.- .1910 .2096 .0005 1897 .0006 3029" 0002--.. .0001 .0005. X-Ray Analysis of Solution:

Test Hours Fe Content, p.p.m Test Hours 48. Fe Content, p.p.m 5.

Solution:

Methanol 95% 95%. TBP 5 5%-. 5% 5%. Additives KM1104 (500 KM1104 MD (0211302): MD(NO3): mg./l.), mg./1.). (100 mg./l.). (0.2 cc./l.). MDA 29 gm./1.).

Test Results: Weight Loss of Metal Specimens Test Hours 187 65%.

Ingot Fe Disc (Gms. Lost) Aluminum Copper 0586. White Metal No Metals Steel" Present 1 4% Or Steel.--

1 01'1 Ingot Iron 0004. X-Ray Analysis of Solution:

Test H0urs Fe Content, pp Test Hours 42 66% Fe.Content,p.p.m 5 43 PercentUnoxidized TBP 4.5 4.0 6.0 5.1 5.0. pH s.s5 9.05 8.1 8.4 7.95.

Nora-TEE is tri-n-butyl phosphine; DBPC is di-butyl para cresol. ingot iron disc present for last hours of test only. NOTIZJr-?M (G2H3O2) is manganous acetate tetrahydrate.

1 Copper strip present for last 42 hours of test showed weight loss of 0.1910 gm. Emiss. spec. analysis of solution showed 300 p.p.m. copper.

Table II Run Number 53 54 55 56 57 58 Solution:

Methanol 90.2 TBP- 4.8... 95 95% 95 95 7 95%. Abs. Alcohol 4.95.. 5%-.. 5 5 5%. Rubber Solvent--- .05 Additives MDA (3cc./ MDA (3co./ MDA (3 cc./1.), MDA (3 cell.) Mn MDA (3 cc./1.), Mn MDA (3 cc./1.), Mn

1.), Mn 1.), Mn Mn (A0); (18.7 (Ac); (16 mg./l. (Ac), (5 mg./l.) (Ac); (2% mg./l.). (Ac): (100 (Ac): (51 mg./l.). mgJl.) mgjl.) Test Results:

Test Hours 66% 66% 66%.. 66 66 66. Specimen Loss- Ingot Iron Disc .0001. .0000 0001 .0002 .0002 .0003. Copper Strip.. 0832 1287 1783.

Solution Analysis:

Time, Hours- 66% 116 138 0 24 48 66 0 24 48 66 0 24 48 66 PercentTBP 4.2 3.9 3.9 5.0 4.9 4.7 5.0 4.9 4.7 4.7 4.9 4.9 4.0 4.6 5.1 nH 7.3 6.92 6.7 8.0 7.92 7.70 7.7 8.05 7.55 7.15 7.1 8.1 7.12 6.9 7.0 ie,p.p.m-. 5 5 5 5 5 5 5 5 5 5 5 5 Norm-TBP is trl-n-butyl phosphine. rubber solvent is a petroleum solvent. Mn(Ac): is manganous acetate tetrahydrate.

I claim:

1. A composition of matter useful as a gasoline additive consisting essentially of from 80 to 98% by volume of methanol and from to 2% by volume of a phosphine of the formula RRR"P wherein R, R and R" are alkyl radicals selected from the group consisting of alkyl radicals containing from 1 to 3 carbon atoms, primary and secondary butyl radicals and primary amyl radicals, the said composition also containing from about 2.5 to 100 mg. per liter of a material selected from the group consisting of potassium permanganate, manganous nitrate, manganous acetate tetrahydrate, anhydrous manganous acetate, manganese dichloride tetrahydrate, manganous oxalate dihydrate, manganous oxalate trihydrate, manganous orthophosphate, trihydrate, manganous sulfate monohydrate, manganous sulfate dihydrate and manganous sulfate trihydrate.

2. The composition of claim 1 wherein RR'R"P is tri-n-butyl phosphine.

3. The composition of claim 1 wherein said material is potassium permanganate.

4. The composition of claim 1 wherein said material is manganous nitrate.

5. The composition of claim 1 wherein said material is manganous acetate tetrahydrate.

6. A composition of matter useful as a gasoline additive consisting essentially of from 80 to 98% by volume of methanol and from 20 to 2% by volume of a phos- 5o phine of the formula RR'R"P wherein R, R' and R" are alkyl radicals selected from the group consisting of alkyl radicals containing from 1 to 3 carbon atoms, primary and secondary butyl radicals and primary amyl radicals, the said composition also containing 15 to mg. per liter of a material selected from the group consisting of potassium permanganate, manganous nitrate, manganous acetate tetrahydrate, anhydrous manganous acetate, manganese dichloride tetrahydrate, manganous oxalate dihydrate, manganous oxalate trihydrate, manganous orthophosphate trihydrate, manganous sulfate monohydrate, manganous sulfate dihydrate and manganous sulfate trihydrate.

7. The composition of claim 6 wherein RR'R"P is tri-n-butyl phosphine and wherein said material is potassium permanganate.

8. The composition of claim 6 wherein RR'RP is tri-n-butyl phosphine and wherein said material is manganous nitrate.

9. The composition of claim 6 wherein RR'R"? is tri-n-butyl phosphine and wherein said material is manganous acetate tetrahydrate.

References Cited in the file of this patent UNITED STATES PATENTS 2,102,825 Woodhouse et al. Dec. 21, 1937 2,197,836 Reiif et al. Apr. 23, 1940 2,797,153 Bereslavsky June 25, 1957 

1. A COMPOSITION OF MATTER USEFUL AS A GASOLINE ADDITIVE CONSISTING ESSENTIALLY OF FROM 80 TO 98% BY VOLUME OF METHANOLD AND FROM 20 TO 2% BY VOLUME OF A PHOSPHINE OF THE FORMULA RR''R"P WHERIN R, R'' AND R" ARE ALKYL SELECTED FROM THE GROUP CONSISTING OF ALKYL CONTAINING FROM 1 TO 3 CARBON ATOMS, PRIMARY AND SECONDARY BUTYL RADICALS AND PRIMARY AMYL RADICALS, THE SAID COMPOSITION ALSO CONTAINING FORM ABOUT 2.5 TO 100 MG. PER LITER OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF POTASSIUM PERMANGANATE, MANGANOUS NITRATE, MANGANOUS ACETATE TETRAHYDRATE, ANHYDROUS MANGANOUS ACETATE, MANGANESE DICHLORIDE TETRAHYDRATE, MANAGANOUS OXALATE DIHYDRATE, MANGANOUS OXALATE TRIHYDRATE, MANGANOUS ORTHOPHOSPHATE, TRIHYDRATE, MANGANOUS SULFER MONOHYDRATE, MANGAMOUS SULFATE DIHYDRATE AND MANGANOUS SULFATE TRIHYDRATE. 